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EP1874874B2 - Pigments de lustre perlaire revetus de couches mixtes inorganiques/organiques et leur procede de production - Google Patents
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EP1874874B2 - Pigments de lustre perlaire revetus de couches mixtes inorganiques/organiques et leur procede de production - Google Patents

Pigments de lustre perlaire revetus de couches mixtes inorganiques/organiques et leur procede de production Download PDF

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Publication number
EP1874874B2
EP1874874B2 EP07722891A EP07722891A EP1874874B2 EP 1874874 B2 EP1874874 B2 EP 1874874B2 EP 07722891 A EP07722891 A EP 07722891A EP 07722891 A EP07722891 A EP 07722891A EP 1874874 B2 EP1874874 B2 EP 1874874B2
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EP
European Patent Office
Prior art keywords
organic
inorganic
group
reactive
polymer
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EP07722891A
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German (de)
English (en)
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EP1874874B1 (fr
EP1874874A2 (fr
Inventor
Frank Henglein
Stefan Trummer
Ulrich Schmidt
Peter Krüger
Günter KAUPP
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Eckart GmbH
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Eckart GmbH
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
    • C09C1/0021—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings comprising a core coated with only one layer having a high or low refractive index
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0098—Organic pigments exhibiting interference colours, e.g. nacrous pigments
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/0015—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
    • C09C1/0024—Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings comprising a stack of coating layers with alternating high and low refractive indices, wherein the first coating layer on the core surface has the high refractive index
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C01P2006/66—Hue (H*)
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/10—Interference pigments characterized by the core material
    • C09C2200/1004—Interference pigments characterized by the core material the core comprising at least one inorganic oxide, e.g. Al2O3, TiO2 or SiO2
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/10—Interference pigments characterized by the core material
    • C09C2200/102—Interference pigments characterized by the core material the core consisting of glass or silicate material like mica or clays, e.g. kaolin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/30—Interference pigments characterised by the thickness of the core or layers thereon or by the total thickness of the final pigment particle
    • C09C2200/301—Thickness of the core
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/30—Interference pigments characterised by the thickness of the core or layers thereon or by the total thickness of the final pigment particle
    • C09C2200/307—Thickness of an outermost protective layer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2200/00—Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/40—Interference pigments comprising an outermost surface coating
    • C09C2200/409—Mixed inorganic-organic coating
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2220/00—Methods of preparing the interference pigments
    • C09C2220/10—Wet methods, e.g. co-precipitation

Definitions

  • the invention relates to platelet-shaped pearlescent pigments which are coated with at least one inorganic / organic mixed layer in order to improve their performance and in particular their mechanical properties, as well as processes for their preparation and their use.
  • This inorganic / organic mixed layer consists of at least one at least partially crosslinked inorganic metal oxide component and one organic component. This is at least one organic oligomer and / or polymer which is at least partially covalently linked to the inorganic network via network formers.
  • Excessive shearing may damage the high refractive index oxide coatings on the substrate, thereby affecting the effect properties. This manifests itself, for example, in susceptibility to the incorporation of pearlescent pigments in plastics or the general need to subject pearlescent pigments-in contrast to ordinary colored pigments-to a mild incorporation into wet paints.
  • pearlescent pigments When incorporated into plastics, pearlescent pigments are extruded in a plastic melt. Chipping the oxide coatings lead to a reduced transparency of the colored plastic and reduced gloss.
  • pearlescent pigments can not be incorporated into the basecoat of a powder coating like colored pigments by extrusion and subsequent grinding in a pin mill. Here they are usually crushed in such a way that the characteristic optical effects are virtually completely lost.
  • the advantageous properties of purely inorganic or purely organic three-dimensionally crosslinked coatings of pearlescent pigments are to be distinguished from various surface treatments. Such surface treatments always aim at the improvement of performance properties which are influenced by the surface chemistry of the pearlescent pigments.
  • an organic surface modification of, for example, inorganic coatings of pearlescent pigments has hitherto been carried out only in the form of a surface modification.
  • the DE 198 20 112 A1 describes reactive organic orienting agents which can chemically bind with a functional group on the surface of a pearlescent pigment and bind to the paint with another functional group.
  • the organic orienting agents are applied to pearlescent pigments provided with inorganic oxide layers or organic polymer layers.
  • no mixed layer of an inorganic oxide / hydroxide and an organic oligomer and / or polymer is built up.
  • the organic orientation agent used only changes the surface properties of the pearlescent pigment.
  • the essential for the optical effect orientation of the platelet-shaped pearlescent pigments in the paint and other performance properties such as condensation resistance and dispersibility in the paint system are favorably influenced.
  • modified pearlescent pigments based on a metal oxide coated, platelet-shaped substrate containing on the topmost metal oxide layer, a top layer of at least two oxides, mixed oxides or mixed oxides of silica, alumina, ceria, titania or zirconia and a water-based oligomeric silane system.
  • An oligomeric silane system is understood here to mean a system of different organofunctional silanes which are linked to one another via the inorganic -Si-O-Si units. Not described, however, are oligomers in which the organic functions of the silanes are covalently linked to one another. Thus, with such Silane systems no organic oligomer and / or polymer network built.
  • the EP 632 109 B1 describes a coating consisting of at least three layers of a pearlescent pigment.
  • the first layer consists of SiO 2 .
  • the second layer consists of at least one hydroxide or oxide of the elements cerium, aluminum or zirconium.
  • the third layer consists of one or more oxides / hydroxides of the elements Ce, Al or Zr and an organic coupling reagent.
  • organically modified silanes are mentioned as coupling reagents.
  • Such coatings give weatherproof pearlescent pigments with improved performance properties.
  • Pearlescent pigments can be improved by a coating with SiO 2 or other inorganic substances in a variety of ways in their performance properties and thereby adapted for a variety of applications.
  • a disadvantage is the inherent brittleness in these purely inorganic coatings. It has been found that under heavy mechanical stress these layers can be damaged resulting in a loss of the desired properties.
  • Mechanical damage to the protective layer can also occur in the case of too vigorous dispersion of pearlescent pigments in a lacquer or in dispersion of pearlescent pigments in extruders for applications in plastics.
  • the object of the present invention is to provide pearlescent pigments having improved mechanical properties.
  • the pearlescent pigments should have good optical properties in the application medium even after the action of strong shear forces.
  • the pearlescent pigments should have a protective layer, which in particular allows weather stability.
  • the object underlying the invention is achieved by a pearlescent pigment according to claim 1. Preferred developments are specified in the subclaims 2-17. The object is further achieved by a method according to claim 18. In the dependent claims 19 - 37 preferred developments of the method according to the invention are given.
  • the at least one inorganic network former, the at least one organic network former and the at least one reactive organic component can be mixed together in any order.
  • the reaction conditions should be adjusted so that a reaction between the components can take place.
  • the reaction preferably takes place by hydrolysis and / or condensation of the components with one another.
  • the components are therefore hydrolyzable and / or condensable.
  • the coating composition forming upon hydrolysis and / or condensation is then applied to the pearlescent pigment surface, preferably by precipitation.
  • the pearlescent pigments may be added to the liquid phase before, during or after adding or reacting the at least one inorganic network former and the at least one organic network former and the at least one reactive organic component.
  • the pearlescent pigments may be initially charged in a liquid phase and subsequently the inorganic network former or monomers, the organic network former (s) and the reactive organic component (s) may be added in any order.
  • the pearlescent pigments may also be added to the coating composition during the reaction or after the reaction.
  • a predominantly inorganic or predominantly organic layer can first be applied to the pearlescent pigment surface before the inorganic / organic mixed layer is applied.
  • the inorganic / organic layer can also be applied directly to the uncoated or precoated pearlescent pigment surface.
  • inorganic network-forming agent is understood to mean that the inorganic network-forming agent can build up an inorganic network.
  • An inorganic network former may be, for example, a hydrolyzable metal salt or a fully hydrolyzable organometallic compound.
  • an organic network former is understood to mean that the organic network former in conjunction with a reactive organic component can build up an organic or organometallic network.
  • An organic network former is preferably an organometallic compound which is only partially hydrolyzable and thus can not build up an inorganic network.
  • the object underlying the invention is also achieved by the use of the platelet-shaped pearlescent pigment according to one of claims 1 to 17 in paints, automotive coatings, paints, printing inks, powder coatings, architectural paints, plastics, security printing inks, ceramics, glass or cosmetic preparations.
  • the object underlying the invention is further achieved by the use of the platelet-shaped pearlescent pigment according to one of claims 1 to 17 as a laser marker.
  • inorganic / organic mixed layer it is possible with an inorganic / organic mixed layer to achieve improved weather stability of pearlescent pigments in comparison to pure inorganic or organic layers.
  • the invention therefore relates to pearlescent pigments which comprise at least one coating comprising an inorganic / organic mixed layer, the mixed layer at least partially comprising an inorganic network comprising one or more inorganic oxide component (s) and at least one organic component the organic component is an organic oligomer and / or polymer which is at least partially covalently linked to the inorganic network via one or more organic network formers.
  • the at least partially covalent connection of the inorganic oxide network with the organic oligomer and / or polymer takes place via at least one organic network former.
  • organic network former reagents that can bind to both the inorganic network and to the organic oligomer and / or polymer.
  • the oxidation number III, zirconium, the oxidation number II, III or IV, and titanium may have the oxidation number II, III or IV.
  • both zirconium and titanium have the oxidation number IV.
  • the reactive group R 1 or the reactive organic radical R 1 is polymerizable according to the invention.
  • the radical R 1 can be polymerizable, for example, with further radicals R 1 , so that the organic network former can be present as such in an oligomerized or polymerized form in the inorganic / organic mixed layer.
  • the radical R 1 may also be polymerizable with other monomers, so that the organic network former in the inorganic / organic mixed layer can be present in polymerized form in a polymer which is also composed of further monomers.
  • organofunctional silanes are particularly preferred. These may bind to the inorganic network after hydrolysis of the hydrolyzable group X. As a result of the hydrolysis, the group X is generally replaced by an OH group, which then forms a covalent bond when it condenses with OH groups of the inorganic network.
  • the group X preferably represents halogen, hydroxy, alkoxy having 1-10 C atoms, which may be straight-chain or branched, may have in the carbon chain, and mixtures thereof.
  • the organic network former binds at least via the functional group R 1 with or to the organic oligomer and / or polymer.
  • R 1 is a reactive functional group.
  • the reactive, polymerizable, organic group R 1 has one or more substituents selected from the group consisting of amino, hydroxy, thiol, epoxy, acrylate, methacrylate, vinyl, allyl, alkenyl , Alkynyl, carboxy, carboxyl anhydride, isocyanate, cyanate, ureido, carbamate and mixtures thereof.
  • the organic radical R 1 is preferably connected to the central silicon atom via a covalent C-Si bond.
  • the radicals R 2 and R 3 are independently selected from the group consisting of H, (C 1 -C 40 ) -alkyl, (C 1 -C 40 ) -fluorinated alkyl, (C 1 -C 40 ) - partially fluorinated alkyl; (C 2 -C 40 ) alkenyl, (C 2 -C 40 ) alkynyl; (C 6 -C 36 ) aryl, fluorinated (C 6 -C 36 ) aryl, partially fluorinated (C 6 -C 36 ) aryl; (C 7 -C 40 ) -alkylaryl, (C 7 -C 40 ) -arylalkyl, fluorinated (C 7 -C 40 ) -alkylaryl, partially fluorinated (C 7 -C 40 ) -alkylaryl; (C 8 -C 40 ) alkenylaryl, (C 8 -C 40 ) arylalkyn
  • the radicals R 2 and R 3 preferably have chain lengths of 3 to 20 carbon atoms, more preferably 5 to 18 carbon atoms.
  • the radicals R 2 and R 3 may be branched and / or linear. In the case of alkyl chains, these may be interrupted by heteroatoms such as O, S, or N.
  • the organic group or the radical R 1 has a reactivity which allows a covalent bond of the organic oligomer and / or polymer.
  • the organic groups or radicals R 2 and / or R 3 can also have a reactivity which allows a covalent bond of the organic oligomer and / or polymer.
  • the radicals R 2 and / or R 3 may also be non-reactive.
  • the radicals R 2 and R 3 are preferably not polymerizable under the applied reaction conditions.
  • the radicals R 2 and R 3, in contrast to the radical R 1, do not polymerize with one another and, in particular under the reaction conditions applied, can not be reacted with monomers to give a polymer.
  • Suitable organofunctional silanes are, for example, many representatives of the products manufactured by Degussa (Sche Kanalstrasse 3, D-79618 Rheinfelden) and marketed under the trade name "Dynasylan".
  • 3-methacryloxypropyltrimethoxysilane (Dynasylan MEMO) can be used to form a (meth) acrylate or polyester, vinyltri (m) ethoxysilane (Dynasylan VTMO or VTEO) to form a vinyl polymer, 3-mercaptopropyltri (m) ethoxysilane (Dynasylan MTMO or 3201)
  • Polymerization into rubber polymers aminopropyltrimethoxysilane (Dynasylan AMMO) or N2-aminoethyl-3-aminopropyltrimethoxysilane (Dynasylan DAMO) to build up a ⁇ -hydroxyamine or 3-g
  • the reactive organic groups are separated from the Si atom by only one methylene unit. They are distinguished from the conventional silanes by accelerated hydrolysis and condensation rates.
  • Suitable organic network formers according to claim 1 also suitable organofunctional titanates, zirconates or aluminates can be used, as prepared for example by Kenrich Petrochemicals and offered under the trade name Ken-React ® . (available from Nordmann, Rassmann GmbH, Kajen 2, 20459 Hamburg).
  • Ken-React ® available from Nordmann, Rassmann GmbH, Kajen 2, 20459 Hamburg.
  • titanates, zirconates and aluminates Coupling Agents, 2nd Revised edition, the summer of 1993 on pages 2 to 21 specified coupling reagents can be used for the most part as organic network.
  • the disclosure of the pages 2 to 21 of the aforementioned KEN-REACT ® Reference Manual is hereby incorporated by reference.
  • organic network formers preferably have as hydrolyzable or condensable group X preferably alkoxy, but also hydroxy or halogen.
  • hydrolyzable or condensable group X preferably alkoxy, but also hydroxy or halogen.
  • alkoxy there may also be a cyclic group bonded to the central atom M via two oxygen atoms, such as oxoethylene or cycloneopentyl.
  • the central atom M has in this case only two further substituents.
  • the hydrolyzable group can also be part of a cyclic unit, which are coordinately bonded via further oxygen atoms to the central atom, and thus can not be cleaved off the molecule after hydrolysis.
  • organophosphite ligands there may be two organophosphite ligands coordinately attached to the central atom. In this case, four alkoxy ligands are attached to the central atom.
  • Al, Zr or Ti organic network formers may be in the form of chelate complexes or coordination complexes.
  • the ligands may contain heteroatoms, preferably N, S or O.
  • the inorganic component of the mixed layer preferably consists of metal oxide and / or metal oxide hydrate and / or metal suboxide and / or metal hydroxide, which at least partially forms a two- or three-dimensional network with one another.
  • the inorganic portion of the mixed layer of metal oxide and / or metal suboxide and / or metal hydroxide is selected from the group consisting of silicon, aluminum, titanium, zirconium, cerium, chromium, manganese, antimony, zinc, boron, magnesium and iron and mixtures and alloys thereof.
  • these oxides are preferably used alkoxides, hydroxides and halides of these compounds.
  • the inorganic network formers have the general formula MX n , where X is independently of one another an optionally hydrolyzable and / or condensable group of halogen, hydroxy or alkoxy having 1-10 C atoms, where the alkoxy group in the carbon chain can have heteroatoms, preferably O, S and / or N, in the carbon chain, is.
  • Ti, Zr, Fe, X may also be chelating ligands such as acetylacetonates or acetoacetic acid esters.
  • inorganic network formers in which M is Si, Al, Ti and / or Zr and X is alkoxy groups having 1 to 6 C atoms, where the alkoxy group in the carbon chain is heteroatoms, preferably O, S and / or N, in may have the carbon chain is.
  • tetraalkoxysilanes in particular tetramethoxy- and / or tetraethoxysilanes, to build up an SiO 2 layer.
  • Pearlescent pigments in particular pearlescent pigments containing one or more iron oxide layers, which are provided with a preferred mixed layer of SiO 2 and acrylate and / or methacrylate, are very stable mechanically.
  • Pearlescent pigments containing one or more titanium dioxide layers are machanically very stable with this preferred mixed layer and are also weather-stable. It has been found that these properties can be further improved if, when the inorganic network is formed, for example by hydrolysis of tetraethoxysilane, acrylic silane and acrylic monomer and / or methacrylic monomer are added.
  • an inorganic oxide network and an organic oligomer and / or polymer can be formed at the same time in a targeted manner.
  • the inorganic network and the organic oligomers and / or polymers preferably penetrate each other.
  • both an inorganic network and an organic network of oligomers and / or polymers are present, which preferably penetrate one another.
  • the inorganic / organic mixed layer can be formed substantially homogeneously.
  • small areas of inorganic network and / or organic oligomer and / or polymer may also be present in the mixed layer.
  • organic oligomers in the mixed layer is meant in this invention the term commonly used in polymer chemistry: i. the linking of two to twenty monomer units (Hans-Georg Elias, "Makromolekule” 4th edition 1981, Hüthig & Wepf Verlag Basel). Polymers are linkages of more than twenty monomer units.
  • the ratio of monomer concentration to the concentration of the organic network formers makes it possible to vary the average chain length of the organic segments.
  • coatings can be produced which impart tailored properties to the pearlescent pigments in many respects.
  • the average chain length of the organic segments is 2 to 10,000, preferably 4 to 5,000, particularly preferably 10 to 1,000 and particularly preferably 40 to 200 monomer units.
  • organic polymers having average chain lengths of from 21 to 15,000, preferably from 50 to 5,000 and particularly preferably from 100 to 1,000 monomer units, are particularly preferably used as the organic component.
  • the organic oligomer and / or polymer in the mixed layer is built up by framework molecules customary in organic polymer chemistry. These are, for example, C-C bonds, amides, esters, acrylates, etc. Siloxanes are not used since silane radicals of the network formers serve to link the inorganic network to the organic network. In addition, the desired mechanical flexibility of the mixed layer can only be achieved by the incorporation of organic framework molecules.
  • the organic oligomer and / or polymer in the mixed layer can preferably be built up by polymerization of suitable monomers.
  • the monomers may have functionalities selected from the group consisting of amino, hydroxy, thiol, epoxy, acrylate, methacrylate, vinyl, allyl, alkenyl, alkynyl, carboxy, carboxylic anhydride, isocyanate , Cyanate, ureido. Carbamate, ester group and mixtures thereof.
  • the inorganic / organic mixed layer is carried out using organic network formers for covalently linking inorganic and organic networks and by polymerizing organic monomers.
  • organic network formers for covalently linking inorganic and organic networks and by polymerizing organic monomers.
  • organic network formers for covalently linking inorganic and organic networks and by polymerizing organic monomers.
  • (Meth) acrylate functions-containing silanes such as Dynasylan MEMO as organic network formers and of methacrylates as monomers.
  • TMPTMA trimethylolpropane trimethacrylate
  • Non-crosslinking (meth) acrylates may also be used as monomers to form the organic component, i. of the organic oligomer and / or polymer, of the mixed layer.
  • the organic component i. of the organic oligomer and / or polymer, of the mixed layer.
  • the most varied possible variations of the chemical composition and thus also of the performance properties of the pearlescent pigments provided with a mixed layer can be made possible.
  • Also suitable are mixtures of crosslinking and monofunctional vinyl and / or (meth) acrylate monomers.
  • Examples of monofunctional (meth) acrylates are: lauryl (meth) acrylate, allyl (meth) acrylate, propyl (meth) acrylate, isobornyl methacrylate and hydroxyethyl imidazoline methacrylate.
  • the polymerization of vinyl and / or (meth) acrylate-functional monomers in the construction of the inorganic / organic mixed layer can also be carried out by ATRP (atomic transfer radical polymerization), the so-called living radical polymerization.
  • ATRP atomic transfer radical polymerization
  • the organic network former it is preferable to use a silane compound in which R 1 is terminally provided with an alkyl halide, preferably an alkyl bromide having an ⁇ -ester group.
  • Cu (I) salts, optionally in admixture with Cu (II) salts or metallic Cu, and suitable ligands complexing the copper compounds are added. Further details can be found in the DE 198 38 241 A1 ,
  • epoxysilanes When using epoxysilanes as organic network formers, these can be reacted with polyfunctional amines as crosslinkers. Further variations are additionally obtained when using polyfunctional epoxy compounds. Combinations of multiply functional epoxy compounds and polyfunctional amino compounds can of course also be used when using amino-functional silanes as coupling reagents.
  • Suitable and commercially available polyfunctional amines suitable for such reactions are, for example: 3,3-dimethyl-4,4-diaminodicyclohexylmethane, ethylenediamine, triethylenetetramine, meta-xylylenediamine, N-aminoethylpiperazine, 2-methyl-1,5-pentamethylenediamine, 1,2-diaminocyclohexane or isophoronediamine.
  • Examples of suitable commercially available multiply functional epoxy compounds are: 1,4-butanediol diglycidyl ether, glycerol triglycidyl ether, neopentyl glycol diglycidyl ether, pentaerythritol polyglycidyl ether, 1,6-hexanediol diglycidyl ether, polypropylene glycol diglycidyl ether or trimethylolpropane triglycidyl ether.
  • the organic network is not prepared during the reaction.
  • the organic component used is reactive organic oligomers and / or polymers which have reactive groups; which permit a connection to the oxide network via the at least one group R 1 of the organic network formers.
  • the oligomer and / or polymer can also be reacted directly with the organic network former prior to incorporation into the mixed layer.
  • the oligomers and / or polymers are dissolved in a suitable solvent, treated with organic network formers and reacted.
  • the organic oligomers and / or polymers coupled to the organic network former can then be reacted with the metal oxide-forming compounds used to form the inorganic network to form the inorganic / organic mixed layer.
  • Reactive organic oligomers and / or polymers which can be incorporated directly into the inorganic network during the reaction are, for example, silane-modified polyethyleneimines or polybutadienes or aminosilane-modified polyethylene oxide urethanes. With such compounds, particularly low molecular weights of 100 to 1000 g / mol are preferred. Low molecular weight compounds of this type have particularly many bonding sites to the inorganic oxide network and thus result in homogeneously distributed inorganic / organic mixed layers.
  • silane-modified phenol-formaldehyde oligomers such as are produced and sold as resoles or novolaks by Bakelite AG (Gennaer Strasse 2-4, D-58642 Iserlohn-Letmathe).
  • compounds which have reactive, preferably polymerizable, functional groups can also be used as reactive oligomers and / or polymers.
  • the polymerizable functional groups can be prepared, for example, by a subsequent reaction of the oligomer and / or polymer (for example by a polymer-analogous reaction). These reactive oligomers / polymers react with the functional organic groups of suitable organic network formers and are thus covalently bonded to the inorganic oxide network (s).
  • reactive oligomers and / or polymers may be reactive polymers from the group of polyacrylates, polymethacrylates, polyethers, polyesters, polyamines, polyamides, polyols, polyurethanes and polyolefins.
  • Organic oligomers and / or polymers which can be incorporated directly into the mixed layer via suitable functional groups are preferably those which have polymer-chemically compatible functional groups to those of the organic network formers.
  • an epoxy group-containing silane an epoxy resin or an amino-containing resin is used
  • (meth) acrylate-containing silanes in the case of (meth) acrylates are used, etc.
  • the reaction of the functional groups of the organic oligomers / polymers with the reactive groups R 1 the organic network forming agent via condensation or addition mechanisms, so the functional groups are preferably coordinated accordingly.
  • epoxy-containing polymers can be particularly well reacted with epoxy- or amino-functionalized silanes. In this way, the polymers are modified by alkoxysilanes and are thus very good together with, for example, tetraalkoxysilanes to inorganic / organic mixed layers can be implemented.
  • prepolymers / proligomers which can be used in this way are the epoxy resin DER: 330 (Dow Corning, Rheingaustr. 53 in D-65201 Wiesbaden, Germany), and also polybutadiene-poly (2,3-epoxy) butadiene copolymer (available from Aldrich, D -89552 Steinheim, Germany).
  • the organic oligomer and / or polymer formation takes place within an inorganic oxide by allowing only the functional groups of the organic network formers to polymerize selectively with one another.
  • network formers in which the polymerizable group R 1 is methacrylate, acrylate or vinyl groups can be polymerized or oligomerized by addition of suitable polymerization initiators.
  • epoxide-containing silanes prior to incorporation into an oxide network in a separate step with each other, for example, to react oligomeric / polymeric polyether units.
  • a mixture of suitable for example, epoxy- and amino-functionalized silanes may react at least in part to form oligomeric / polymeric ⁇ -hydroxyamines before incorporation into the inorganic / organic mixed layer, thereby already forming a quasi-two-dimensional organic network.
  • silane mixtures can then be reacted after oligomerization and / or polymerization with the resulting oxide network to form an inorganic / organic mixed layer.
  • Such inorganic / organic mixed layers formed preferably have a lower degree of polymerization in the organic component than when additional copolymerized organic monomers, i. be additionally added during the polymerization.
  • the organic fraction in the inorganic / organic mixed layer applied to a platelet-shaped substrate is in the range from 4 to 85% by weight, preferably 5 to 75 wt .-% and particularly preferably 10 to 50 wt .-%, wherein the wt .-% by weight refers to the weight of the entire mixed layer.
  • the beneficial i. elasticity-improving effects of the organic oligomer and / or polymer hardly effective.
  • the beneficial i. lost the abrasion resistance-improving effects of the inorganic component.
  • the mechanical stabilization of the inorganic / organic mixed layer is still given at very high layer thicknesses.
  • the layer thickness of the inorganic / organic mixed layer is in a range of about 10 nm to 50 nm.
  • the advantageous effects are still present at a maximum layer thickness of 800 nm, preferably 700 nm and most preferably 600 nm. Layer thicknesses above these ranges increase the overall thickness of the pearlescent pigments too much. In this case, the orientation ability of the pearlescent pigments in the application medium, which is essential for the optical effect formation, is increasingly limited.
  • the layer thickness can be 1.5 to 10 nm, preferably 2 to 5 nm.
  • the two components of the inorganic / organic mixed layer can be present both homogeneously distributed over the thickness of the layer and also inhomogeneous, for example in the form of a gradient distribution, so that the mixing ratio of the two components changes along the layer thickness.
  • the above limits of the composition of the mixed layer apply in the case of an inhomogeneous distribution of the individual components for the mean value along the thickness of the mixed layer.
  • a substantially homogeneous, preferably homogeneous, distribution of inorganic network and organic oligomer and / or polymer is preferred.
  • the organic oligomers and / or polymers may, for example, also be present at least partially in the form of nanoparticles in the inorganic network with formation of the inorganic / organic mixed layer.
  • the inorganic oxide component it is also possible for the inorganic oxide component to be present at least partially in the form of nanoparticles in the organic oligomer and / or polymer to form the inorganic / organic mixed layer.
  • the inorganic / organic mixed layer in the nanoscale region has a substantially homogeneous structure, so that the formation of inorganic nanoparticles in a substantially organic environment of oligomer and / or polymer or of organic nanoparticles in the form of oligomer and / or polymer occurs less frequently in an inorganic environment.
  • a homogeneous structure is obtained in particular when using a high proportion of organic network forming agents in the production of the inorganic / organic mixed layer.
  • the pearlescent pigments usable as platelet-shaped substrate have a platelet-shaped, transparent substrate core, which preferably consists of the group consisting of mica, talc, sericite, kaolin and SiO 2 , glass, graphite, Al 2 O 3 platelets and mixtures thereof, is selected.
  • Preferred Substratkeme here are natural or synthetic mica, SiO 2 , glass, or Al 2 O 3 platelets.
  • the transparent substrate core is preferably made of low-refractive index material, where low-refractive index ⁇ 1.8 is to be understood.
  • Such layers are preferably selected from the group consisting of metal chalcogenides, in particular metal oxides, metal hydroxides, metal oxide hydrates, metal suboxides and metal sulfides, metal fluorides, metal nitrides, metal carbides and mixtures thereof.
  • the substrate bodies of the pearlescent pigments are preferably coated with a multilayered layer structure with or consisting of high refractive index metal oxide, metal hydroxide, metal suboxide and / or metal oxide hydrate, the sequence of the layers being variable.
  • the metal oxides, metal hydroxides, metal suboxides and / or metal oxide hydrates can also be present side by side in the same layer.
  • the refractive index of the high refractive index metal oxide layer is, to give a good pearlescent effect, greater than 1.8, preferably greater than 2.2, more preferably greater than 2.3, even more preferably greater than 2.4, and most preferably 2.5 or larger.
  • the substrate cores of the pearlescent pigments with one or more high-refractive index metal oxide layers from the group consisting of or comprising TiO 2 , Fe 2 O 3 , Fe 3 O 4 , TiFe 2 O 5 , ZnO, SnO 2 , CoO, Co 3 O 4 are preferred , ZrO 2 , Cr 2 O 3 VO 2 , V 2 O 3 , (Sn, Sb) O 2 and mixtures thereof.
  • Particularly preferred are TiO 2 and / or Fe 2 O 3 .
  • Particularly preferred is TiO 2 in the rutile modification.
  • the multilayered layer structure has a layer sequence in which at least one high-index layer and at least one low-index layer are arranged in an alternating manner on a substrate core.
  • the at least one high-index layer of metal oxide and / or metal hydroxide preferably contains or consists of the group consisting of TiO 2 , Fe 2 O 3 , Fe 3 O 4 , TiFe 2 O 5 , ZnO, SnO 2 , CoO, Co 3 O 4 , ZrO 2 , Cr 2 O 3 VO 2 , V 2 O 3 , (Sn, Sb) O 2 and mixtures thereof.
  • the low refractive index layer preferably contains or consists of metal oxide and / or metal hydroxide from the group consisting of SiO 2 , Al 2 O 3 , B 2 O 3 and mixtures thereof.
  • Pearlescent pigments which have high and low refractive layers, give particularly intense interference colors.
  • pearlescent pigments with a high-refractive and a low-refractive and in turn a high-refractive-index layer are particularly preferred.
  • a layer sequence with or made of TiO 2 / SiO 2 / TiO 2 and optional even a layer of Fe 2 O 3 can give intense gold tones and are particularly preferred.
  • the platelet-shaped substrates consist of glass platelets as substrate cores, which are coated on both sides with semitransparent metal layers.
  • the metals of the semitransparent metal layers are preferably selected from the group consisting of silver, aluminum, chromium, nickel, gold, platinum, palladium, copper, zinc, their mixtures and their alloys.
  • the thicknesses of the semitransparent layers are preferably in a range from about 2 to about 30 nm, more preferably from about 5 to about 20 nm.
  • TiO 2 -coated substrate cores are preferably provided with the above-described inorganic / organic mixed layer.
  • Coated with TiO 2 and / or iron oxide mica pigments are, for example, under the name PHOENIX ® (Fa. Eckart) are commercially available.
  • TiO 2 and / or Fe 2 O 3 coated Al 2 O 3 flakes are sold under the trade name Xirallic ® and accordingly SiO 2 flakes coated under the trade name Colorstream ® by the company.
  • Merck offered.
  • Coated with TiO 2 and / or iron oxide glass flakes are offered for example by the company. Engelhard, USA under the name Fire Mist ® or by the company. Merck, Darmstadt, under the name MIRAVAL ®.
  • multi-layered interference pigments such as those in the DE 19618569 can be described, consisting of a carrier material which is coated with alternating layers of metal oxides with low and high refractive index, can be coated according to the invention.
  • Platelet-shaped are the substrates having a shape factor (ratio of the mean value of the longitudinal extent to the thickness) of 3 to 10,000, preferably from 5 to 5,000 and most preferably from 10 to 4,500.
  • the size ratios of the platelet-shaped substrates are characterized by the mean value (d 50 value) of the cumulative distribution curve as usually measured by laser diffraction methods. In this case, preference is given to sizes having a d 50 of from 0.5 to 2,000 ⁇ m, particularly preferably from 1 to 1,500 ⁇ m and very particularly preferably from 2 to 1,000 ⁇ m.
  • the transparent substrates can firstly be provided with one or more coatings, which are either of inorganic or organic nature only, before the mixed layer is applied.
  • coatings which are either of inorganic or organic nature only.
  • the preparation of such layers is well known to those skilled in the art.
  • Metal oxide layers are preferred here. Particularly preferred are metal oxide containing SiO 2, or consist thereof. Another preferred variant consists of a cerium oxide layer which is followed by a SiO 2 layer. Such layer sequences are extremely advantageous, in particular with weather-stable pearlescent pigments.
  • Metal oxide layers are likewise preferred here. Particularly preferred are metal oxide layers containing or consisting of SiO 2 .
  • the layer thicknesses of the purely inorganic or organic layers are between 2 and 1000 nm, preferably between 5 and 500 nm and very particularly preferably between 7 and 50 nm.
  • purely inorganic layers are meant here layers with an organic content below 4% by weight.
  • purely organic layers are meant layers having an inorganic content below 4% by weight. The above data in% by weight are based on the weight of each layer.
  • the reaction conditions for the coating with purely inorganic or organic layers before or after application of the mixed layer may possibly differ from those required for the mixed layer formation.
  • the reaction temperature, the solvent or the pH can be changed. This may possibly require a termination of the reaction and a work-up of the precursor, for example by filtration and drying in vacuo before or after the precipitation of the inorganic / organic mixed layer on the substrate.
  • the coating with a purely inorganic layer or a purely organic layer in the same medium as the coating with the inorganic-organic mixed layer is carried out as a one-pot reaction.
  • the performance advantages of the increased mechanical stability of the inorganic / organic mixed layer are largely independent of whether further purely inorganic or purely organic layers are present between the transparent substrate and the mixed layer and / or on the mixed layer itself. It may be advantageous to begin with the coating initially only with the inorganic component. In this way, a better adhesion of the subsequent mixing layer on the substrate can be effected. This is especially true when the mixed layer has very hydrophobic components such as organic fluorinated functionalities.
  • Another coating of the mixed layer with an example pure oxide layer is also advantageous. On this oxide layer, a desired surface modification may under certain circumstances be carried out much better than is possibly possible with the mixed layer. This is especially true when the mixed layer has very hydrophobic components and / or has a very high content of organic oligomer and / or polymer (for example> 20% by weight).
  • the pearlescent pigments which have an inorganic / organic mixed layer, can be provided with a surface modifier.
  • a surface modifier are for example already in the DE 198 20 112 known.
  • the pearlescent pigments can be designed in their application properties compatible with the particular application medium used, for example, a paint or a printing ink.
  • an improvement in the mechanical stabilization of a coating by surface modification alone can not be achieved.
  • the addition of the surface modifier can also be carried out following the precipitation of the inorganic / organic mixed layer or the precipitation of one or more further inorganic layers in the same solvent.
  • the surface modifier can be dissolved in a suitable solvent and then applied in a mixer to the pearlescent pigments. It is also possible to apply the surface modifier, if appropriate in dry form, to the pearlescent pigments according to the invention, for example by Spray drying.
  • the process according to the invention can be carried out according to a variant, thus on the basis of steps (a), (b1), (c1), (d1), (e) and (f) or on the basis of steps (a), (b2), (c2 ), (d2), (e) and (f).
  • the at least one reactive organic component is preferably added in the form of reactive polymerisable organic monomers, oligomers and / or polymers.
  • At least one reactive oligomer and / or polymer is added as the reactive organic component.
  • the reactive oligomer and / or polymer is selected from the group consisting of polyacrylates, polymethacrylates, polyethers, polyesters, polyamines, polyamides, polyols, polyurethanes, polyolefins and mixtures thereof and optionally for activation Addition in the reaction mixture or in the liquid phase reacted with an organic network former.
  • the reactive organic component is formed prior to addition by reacting one or more different organic network formers having reactive groups R 1 with one another, optionally with the addition of polymerization initiators, and then adding them.
  • the reactive organic oligomer and / or polymer is selected from the group consisting of silanol- and / or methoxy-terminated silicones, polyarylalkylsilsesquioxanes, trialkoxysilane-modified polyethyleneimines, and aminosilane-modified polyethyleneoxyurethanes.
  • the reactive organic oligomer and / or polymer is selected from the group consisting of polyacrylates, polymethacrylates, polyethers, polyesters, polyamines, polyamides, polyols, polyurethanes and polyolefins, these oligomers and / or polymers have reactive, non-polymerized functions.
  • At least one organic network converter is additionally added before, during and / or after the addition of the reactive organic component.
  • aqueous and / or organic solvents or solvent mixtures can be used as the liquid phase.
  • organic solvents in the form of alcoholic solutions which have a water content of from 1 to 80% by weight, preferably from 2 to 30% by weight and more preferably from 3 to 10% by weight.
  • a content of at least 1% by weight of water is necessary to hydrolyze the organic and inorganic network formers.
  • the indication wt .-% refers in each case to the total weight of the solvent.
  • organic solvents it is possible to use all customary solvents such as alcohols, ethers, ketones, esters, glycols or hydrocarbons or mixtures thereof.
  • alcohols for example, methanol, ethanol, n-propanol, isopropanol, n-butanol or 2-butanol or mixtures thereof are used.
  • the steps (b) to (e) of the coating reaction occur at reaction temperatures in a range from about 0 ° C to about 100 ° C, preferably from about 10 ° C to about 80 ° C.
  • the reaction temperatures are limited by the boiling point of the solvent or solvent mixture used.
  • the pH in steps (b) to (e) is in a range of from 3 to 12, preferably from 6 to 10.
  • the pearlescent pigments coated according to the invention can be subjected to size classification, for example by sieving. Furthermore, they can be dried in a suitable aggregate. After separation of the pigments from the reaction mixture, a solvent change is possible in which a solvent other than that used for the reaction is added to the dried pigment powder. In this way it is possible to prepare pastes which have a pearlescent pigment content of 50 to 90% by weight, preferably of 60 to 75% by weight, the statement% by weight being based on the weight of the paste.
  • the pearlescent pigments coated according to the invention are used in paints, inks, printing inks, powder coatings, plastics, security printing inks, glass and ceramics, architectural paints or cosmetics. Furthermore, they are used as laser markers.
  • Comparative Example 2 Iron oxide-coated mica (PHOENIX PX 1542, Eckart), without further aftertreatment.
  • Solution A 5.0 g of 25% aqueous NH 4 OH, dissolved in 150 ml of isopropanol.
  • the samples were extruded at various temperatures. They were each exposed to the extrusion temperature for about 5 minutes.
  • Table 1 clearly shows the significantly better transparency of the plastic applications of the example according to the invention in comparison with the comparative examples.
  • the proportion of fine fraction is correspondingly lower.
  • some mechanical stabilization also takes place by coating an iron oxide-containing pearlescent pigment with SiO 2 (Comparative Example 3 in comparison to Comparative Example 2), the stabilizing effect of the organic / inorganic mixed layer according to the invention is significantly higher.
  • the pigment has a theoretical Ce content of 0.7% by weight and an SiO 2 content of 5.5% by weight. It was determined a carbon content of 1.2 wt .-%.
  • the pigment has a theoretical cerium content of 0.7 wt .-% and a SiO 2 content of 6.0 wt .-%. It was determined a carbon content of 1.8 wt .-%.
  • Example 8 as in Example 6 but without cerium deposition:
  • the pigment has a theoretical SiO 2 content of 5.5% by weight. It became a carbon content of 1.1 % By weight determined.
  • Example 9 as Ex. 8, with organ. Surface modification:
  • the pigment has a theoretical SiO 2 content of 6.0% by weight. It was determined a carbon content of 1.7 wt .-%.
  • This test was based on the in the EP 0 870 730 described UV test for determining the UV activity of TiO 2 pigments as a rapid test for photochemical activity.
  • 1.0 g of the pearlescent pigments according to the invention after-treated according to Examples 6 and 8 without organic surface modification were dispersed in 9.0 g of a double-bond-rich melamine-containing varnish.
  • Squeegee prints (wet film thickness: 100 ⁇ m) were made on paper and dried at room temperature. The squeegee prints were divided and stored in each case one of the two sections as an unloaded reference sample in the dark.
  • the pigment samples were incorporated into a commercially available water-based paint system and the test applications produced by spray painting.
  • the basecoat was overcoated with a commercial 1K clearcoat and then baked.
  • the samples were weathered by means of a condensation water test in accordance with DIN 50017 and evaluated immediately and one hour after the end of the stress.
  • a coating according to the invention can therefore also significantly improve the weather and UV stability of the pearlescent pigments investigated, as a comparison of the test results with the comparative example 11 representing the prior art shows.

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  • Organic Chemistry (AREA)
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  • Adornments (AREA)

Claims (39)

  1. Pigments à lustre nacré présentant un revêtement comprenant un substrat transparent plaquettaire, caractérisé en ce que le revêtement comprend au moins une couche mixte anorganique / organique, la couche mixte présentant au moins partiellement un réseau anorganique qui présente un ou plusieurs composant(s) d'oxyde anorganique et au moins un composant organique, le composant organique étant un oligomère et/ou polymère organique qui est lié de façon covalente au moins en partie avec le réseau anorganique par un ou plusieurs agents de réticulation, la liaison covalente au moins partielle de composants d'oxyde anorganique et d'oligomère et/ou polymère organique s'effectuant au moins en partie par un ou plusieurs agents de réticulation organiques qui présentent la formule générale (I)

            R1 nR2 mR3 oSiX (4-n-m-o)     (I)

    X étant un groupe hydrolysable après l'hydrolyse duquel une liaison covalente d'agents de réticulation organique peut être formée avec le réseau anorganique,
    et R1 désignant un groupe organique réactif qui peut être lié de façon covalente avec l'oligomère et/ou polymère organique,
    R2 et R3 étant indépendamment l'un de l'autre, respectivement un groupe organique, qui peuvent être liés de façon covalente avec l'oligomère et/ou le polymère organique,
    à condition que
    n, m et o soient des nombres entiers, sachant que n+m+o = 1-3 et n = 1 à 3, m = 0 à 2 et o = 0 à 2,
    et/ou la formule générale (II)

            (R1O)n(R2O)m(R3O)oMX(k-n-m-o)     (II)

    la liaison pouvant être au moins un groupe X hydrolysable après l'hydrolyse duquel, une liaison covalente de l'agent de réticulation organique peut être formée avec le réseau anorganique, au moins un radical organique R1 qui désigne un groupe organique réactif qui peut être lié de façon covalente avec l'oligomère et/ou le polymère organique et R2 et R3 pouvant être indépendamment l'un de l'autre, respectivement, un groupe organique, qui peuvent être liés de façon covalente avec l'oligomère organique et/ou polymère,
    k étant l'indice d'oxydation formel de M,
    M étant Al, Zr ou Ti,
    n étant un nombre entier de 1 à (k-1) m étant un nombre entier de 0 à (k-2),
    o étant un nombre entier de 0 à (k-2), et
    n+m+o étant un nombre entier de 1 à k-1,
    R1 étant un radical organique réactif qui présente un ou plusieurs substituants qui sont choisis dans le groupe comprenant les groupes amino, hydroxy, thiol, époxy, acrylate, méthacrylate, vinyle, allyle, alcényle, alcinyle, carboxy, carboxylanhydride, isocyanate, cyanate, uréido, carbamate et leurs mélanges et
    R2 et R3 étant choisis indépendamment dans le groupe comprenant H-, un groupe alkyle (en C1 à C40), alkyle fluoré (en C1 à C40), alkyle partiellement fluoré (en C1 à C40) ; alcényle (en C2 à C40), alcinyle (en C2 à C40), aryle (en C6 à C36), aryle fluoré (en C6 à C36), aryle partiellement fluoré (en C6 à C36) ; alkylaryle (en C7 à C40), arylalkyle (en C7 à C40), alkylaryle fluoré (en C7 à C40), alkylaryle partiellement fluoré (en C7 à C40) ; alcénylaryle (en C6 à C40), arylalcinyle (en C8 à C40) ; alkinylaryle (en C8 à C40) ; cycloalkyle (en C5 à C40), alkylcycloalkyle (en C6 à C40), cycloalkylalkylsilane (en C6 à C40) qui sont substitués respectivement par des groupes amino, hydroxy, thiol, époxy, acrylate, méthacrylate, vinyle, allyle, alcényle, alcinyle, carboxy, carboxylanhydride, isocyanate, cyanate, uréido, carbamate et/ou ester et dans les chaînes de carbone et les systèmes cycliques du carbone, O, N et S peuvent être contenus en tant qu'hétéroatomes, et leurs mélanges, et
    la fraction organique de la couche mixte appliquée sur le substrat plaquettaire se situant dans une plage de 4 à 85 % en poids par rapport au poids de la couche mixte totale.
  2. Pigments à lustre nacré selon la revendication 1,
    caractérisés en ce
    que les composants d'oxyde anorganique de la couche mixte sont choisis dans le groupe comprenant l'oxyde métallique, le suboxyde métallique, l'hydroxyde métallique, l'hydrate d'oxyde métallique et leurs mélanges.
  3. Pigments à lustre nacré selon la revendication 2,
    caractérisés en ce
    que les composants d'oxyde anorganique de la couche mixte sont choisis parmi l'oxyde métallique et/ou le suboxyde métallique et/ou l'hydrate d'oxyde métallique et/ou l'hydroxyde métallique d'éléments du groupe comprenant le silicium, l'aluminium, le titane, le zirconium, le fer, le cérium, le chrome, le manganèse, le zinc, l'étain, l'antimoine, le bore et le magnésium et leurs mélanges.
  4. Pigments à lustre nacré selon l'une quelconque des revendications 1 à 3,
    caractérisés en ce
    que l'agent de réticulation organique est un silane selon la formule générale (I), le/les groupe(s) hydrolysable(s) pouvant être indépendamment l'un de l'autre choisis dans le groupe comprenant un atome d'halogène, un groupe hydroxy, alcoxy comportant 1 à 10 atomes de carbone qui peuvent être à chaîne linéaire ou ramifiée, et leurs mélanges.
  5. Pigments à lustre nacré selon l'une quelconque des revendications 1 à 3,
    caractérisés en ce
    que l'agent de réticulation organique possède la formule générale (II), le/les groupe(s) hydrolysable(s) étant choisis indépendamment dans le groupe comprenant un atome d'halogène, un groupe hydroxy, alcoxy comportant 1 à 20 atomes de carbone, qui peuvent être à chaîne linéaire ou ramifiée, et des hétéroatomes, de préférence O, S et/ou N dans la chaîne de carbone, et leurs mélanges.
  6. Pigments à lustre nacré selon l'une quelconque des revendications précédentes,
    caractérisés en ce
    que l'oligomère et/ou le polymère organique est constitué de monomères présentant les fonctionnalités choisies dans le groupe comprenant les groupes amino, hydroxy, thiol, époxy, acrylate, méthacrylate, vinyle, allyle, alcényle, alcinyle, carboxy, carboxylanhydride, isocyanate, cyanate, uréido et carbamate et leurs mélanges.
  7. Pigments à lustre nacré selon l'une quelconque des revendications 1 à 5,
    caractérisés en ce
    que les composants organiques sont constitués d'oligomères et/ou de polymères organiques réactifs qui présentent des groupes pouvant réagir qui peuvent être liés au réseau anorganique et/ou au moins au groupe R1 des réseaux organiques.
  8. Pigments à lustre nacré selon la revendication 7,
    caractérisés en ce
    que l'oligomère et/ou le polymère organique réactif est choisi dans le groupe comprenant des polyéthylène-imines modifiées par trialcoxysilane et des polyéthylène-oxyde-uréthanes modifiés par aminosilane et leurs mélanges.
  9. Pigments à lustre nacré selon la revendication 7,
    caractérisés en ce
    que l'oligomère et/ou le polymère organique réactif est choisi dans le groupe comprenant des polyacrylates, polyméthacrylates, polyéthers, polyesters, polyamines, polyamides, polyols, polyuréthanes et polyoléfines, ces oligomères et/ou polymères présentant des groupes fonctionnels réactifs qui peuvent se lier au réseau anorganique ou à un agent de réticulation organique.
  10. Pigments à lustre nacré selon l'une quelconque des revendications 1 à 9,
    caractérisés en ce
    que l'oligomère et/ou le polymère organique est lié de façon covalente par le groupe fonctionnel R1 d'un ou plusieurs agents de réticulation organique dans la couche mixte anorganique / organique.
  11. Pigments à lustre nacré selon l'une quelconque des revendications 1 à 10,
    caractérisés en ce
    que le substrat est choisi dans le groupe des pigments à lustre nacré, des pigments à lustre nacré revêtus d'oxydes ou d'oxydes mixtes, des plaquettes de dioxyde de titane, des plaquettes d'oxyde de fer et des pigments d'oxychlorure de bismuth.
  12. Pigments à lustre nacré selon l'une quelconque des revendications précédentes,
    caractérisés en ce
    qu'entre le substrat et la couche mixte anorganique/organique est disposée au moins une couche séparée essentiellement purement anorganique et/ou au moins une couche séparée constituée essentiellement d'un polymère purement organique.
  13. Pigments à lustre nacré selon l'une quelconque des revendications précédentes,
    caractérisés en ce
    que sur la couche mixte anorganique / organique est disposée au moins une couche séparée essentiellement purement anorganique et/ou au moins une couche séparée constituée d'un polymère essentiellement purement organique.
  14. Pigments à lustre nacré selon les revendications 12 ou 13,
    caractérisés en ce
    que les couches séparées essentiellement purement anorganiques sont produites à partir d'oxydes métalliques et/ou d'hydrate d'oxydes métalliques et/ou de suboxydes métalliques et/ou d'hydroxydes métalliques d'éléments choisis dans le groupe comprenant le silicium, le titane, l'aluminium, le zirconium, le fer, le cuivre, l'étain, le cobalt, le chrome, le cérium, le zinc, l'antimoine, le manganèse, le nickel, l'yttrium, le molybdène, le vanadium, le tantale, le wolfram et leurs mélanges.
  15. Pigments à lustre nacré selon les revendications 12 ou 13,
    caractérisés en ce
    qu'au moins une couche polymère séparée essentiellement purement organique est choisie dans le groupe comprenant le polyacrylate, le polyméthacrylate, le polyéther, le polyester, la polyamine, le polyamide, le polyol, le polyuréthane, le polyphénolformaldéhyde, la polyoléfine, le poly-1,2,3,4-tétrafluoroéthylène et leurs mélanges.
  16. Pigments à lustre nacré selon l'une quelconque des revendications précédentes, caractérisés en ce que sur la surface du pigment à lustre nacré revêtu est appliquée en outre une couche comprenant un ou plusieurs agents de modification de surface.
  17. Pigments à lustre nacré selon l'une quelconque des revendications précédentes,
    caractérisés en ce
    que le substrat plaquettaire est choisi dans le groupe comprenant
    des plaquettes de mica revêtues de TiO2 et/ou d'oxyde de fer,
    des plaquettes de verre revêtues de TiO2 et/ou d'oxyde de fer,
    des plaquettes d'oxyde d'aluminium revêtues de TiO2 et/ou d'oxyde de fer,
    des plaquettes de SiO2 revêtues de TiO2 et/ou d'oxyde de fer,
    des plaquettes d'oxychlorure de bismuth,
    des plaquettes de TiO2 pures et
    leurs mélanges.
  18. Procédé de fabrication d'un pigment à lustre nacré avec une couche mixte anorganique / organique qui comprend les étapes suivantes :
    - conversion d'au moins un agent de réticulation anorganique et au moins d'un agent de réticulation organique et au moins d'un composant réactif organique dans une phase liquide en formant une composition de revêtement,
    - application de la composition de revêtement sur des substrats transparents plaquettaires comme couche mixte,
    les substrats métalliques plaquettaires étant ajoutés avant, pendant ou après l'addition ou la conversion d'au moins un agent de réticulation anorganique et d'au moins un agent de réticulation organique et d'au moins un composant organique réactif à la phase liquide,
    la couche mixte présentant au moins en partie un réseau anorganique qui présente un ou plusieurs composant(s) anorganique(s) et au moins un composant organique, les composants organiques étant au moins en partie un oligomère et/ou un polymère organique qui est lié de façon covalente au moins partiellement au réseau anorganique,
    au moins un agent de réticulation organique présentant la formule générale (I)

            R1 nR2 mR3 oSiX (4-n-m-o)     (I)

    X étant un groupe hydrolysable après l'hydrolyse duquel une liaison covalente d'agents de réticulation organique peut être formée avec le réseau anorganique,
    et R1 désignant un groupe organique réactif qui peut être lié de façon covalente avec l'oligomère et/ou polymère organique,
    R2 et R3 étant indépendamment l'un de l'autre, respectivement un groupe organique, qui peuvent être liés de façon covalente avec l'oligomère et/ou le polymère organique,
    à condition que
    n, m et o soient des nombres entiers, sachant que n+m+o = 1-3 et n = 1 à 3, m = 0 à 2 et o = 0 à 2,
    et/ou l'agent de réticulation organique présente la formule générale (II)

            (R1O)n(R2O)m(R3O)oMX (k-n-m-o)     (II)

    la liaison organométallique pouvant être au moins un groupe X hydrolysable après l'hydrolyse duquel, une liaison covalente de l'agent de réticulation organique peut être formée avec le réseau anorganique, au moins un radical organique R1 qui désigne un groupe organique réactif qui peut être lié de façon covalente avec l'oligomère et/ou le polymère organique et R2 et R3 pouvant être indépendamment l'un de l'autre, respectivement, un groupe organique, qui peuvent être liés de façon covalente avec l'oligomère organique et/ou polymère,
    k étant l'indice d'oxydation formel de M,
    M étant Al, Zr ou Ti,
    n étant un nombre entier de 1 à (k-1),
    m étant un nombre entier de 0 à (k-2),
    o étant un nombre entier de 0 à (k-2), et n+m+o étant un nombre entier de 1 à k-1 et
    R1 étant un radical organique réactif qui présente un ou plusieurs substituants qui sont choisis dans le groupe comprenant les groupes amino, hydroxy, thiol, époxy, acrylate, méthacrylate, vinyle, allyle, alcényle, alcinyle, carboxy, carboxylanhydride, isocyanate, cyanate, uréido, carbamate et leurs mélanges et
    R2 et R3 étant choisis indépendamment dans le groupe comprenant H-, un groupe alkyle (en C1 à C40), alkyle fluoré (en C1 à C40), alkyle partiellement fluoré (en C1 à C40) ; alcényle (en C2 à C40), alcinyle (en C2 à C40), aryle (en C6 à C36), aryle fluoré (en C6 à C36), aryle partiellement fluoré (en C6 à C36) ; alkylaryle (en C7 à C40), arylalkyle (en C7 à C40), alkylaryle fluoré (en C7 à C40), alkylaryle partiellement fluoré (en C7 à C40) ; alcénylaryle (en C6 à C40), arylalcinyle (en C8 à C40) ; alkinylaryle (en C6 à C40) ; cycloalkyle (en C5 à C40), alkylcycloalkyle (en C6 à C40), cycloalkylalkylsilane (en C6 à C40) qui sont substitués respectivement par des groupes amino, hydroxy, thiol, époxy, acrylate, méthacrylate, vinyle, allyle, alcényle, alcinyle, carboxy, carboxylanhydride, isocyanate, cyanate, uréido, carbamate et/ou ester et dans les chaînes de carbone et les systèmes cycliques du carbone, O, N et S peuvent être contenus en tant qu'hétéroatomes, et leurs mélanges et
    la fraction organique de la couche mixte appliquée sur le substrat plaquettaire se situant dans une plage de 4 à 95 % en poids par rapport au poids de la couche mixte totale.
  19. Procédé de fabrication d'un pigment à lustre nacré selon la revendication 18 qui comprend les étapes suivantes :
    (a) la mise à disposition d'un mélange réactionnel de substrats transparents plaquettaires dans une phase liquide,
    (b1) l'addition d'au moins un agent de réticulation anorganique à un mélange réactionnel de l'étape (a),
    (c1) l'hydrolyse et/ou la condensation de l'agent de réticulation anorganique ajouté à l'étape (b1),
    (d1) l'addition d'au moins un agent de réticulation organique réactif et d'au moins un composant organique réactif, pendant et/ou après l'hydrolyse et/ou la condensation de l'étape (c1)
    ou
    (b2) l'addition d'au moins un agent de réticulation organique réactif et au moins d'un composant organique réactif au mélange réactionnel de l'étape (a) ;
    (c2) l'addition d'au moins un agent de réticulation anorganique au mélange réactionnel de l'étape (b2),
    (d2) l'hydrolyse et/ou la condensation de l'agent de réticulation anorganique ajouté à l'étape (c2),
    et
    (e) la conversion de l'agent de réticulation anorganique hydrolysé et/ou condensé avec l'agent de réticulation organique réactif et du composant organique réactif par dépôt concomitant et/ou consécutif de la couche mixte anorganique/organique,
    (f) la séparation éventuelle du substrat plaquettaire revêtu à l'étape (e) du mélange réactionnel.
  20. Procédé selon la revendication 18 ou 19,
    caractérisé en ce
    que le composant organique réactif est ajouté sous la forme de monomères, oligomères et/ou polymères organiques polymérisables réactifs.
  21. Procédé selon la revendication 19,
    caractérisé en ce
    que l' on ajoute comme composant organique réactif au moins un oligomère et/ou un polymère réactif.
  22. Procédé selon l'une quelconque des revendications 18 à 21,
    caractérisé en ce
    que les composants d'oxyde anorganiques de la couche mixte sont choisis dans le groupe comprenant l'oxyde métallique, l'hydrate d'oxyde métallique, le suboxyde métallique, l'hydroxyde métallique et leurs mélanges.
  23. Procédé selon l'une quelconque des revendications 18 à 22,
    caractérisé en ce
    que les composants d'oxyde anorganiques de la couche mixte sont choisis dans le groupe comprenant l'oxyde métallique et/ou l'hydrate d'oxyde métallique et/ou le suboxyde métallique et/ou l'hydroxyde métallique d'éléments du groupe comprenant le silicium, l'aluminium, le titane, le zirconium, le fer, le cérium, le chrome, le manganèse, le zinc, l'étain, l'antimoine, le bore et le magnésium et leurs mélanges.
  24. Procédé selon l'une quelconque des revendications 18 à 23,
    caractérisé en ce
    que l'agent de réticulation organique est un silane selon la formule générale (I), le/les groupe(s) hydrolysable(s) pouvant être indépendamment l'un de l'autre choisis dans le groupe comprenant un atome d'halogène, un groupe hydroxy, alcoxy comportant 1 à 10 atomes de carbone qui peuvent être à chaîne linéaire ou ramifiée et leurs mélanges.
  25. Procédé selon l'une quelconque des revendications 18 à 23,
    caractérisé en ce
    que l'agent de réticulation organique possède la formule générale (II), le/les groupe(s) hydrolysable(s) étant choisis indépendamment dans le groupe comprenant un atome d'halogène, un groupe hydroxy, alcoxy comportant 1 à 20 atomes de carbone, qui peuvent être à chaîne linéaire ou ramifiée, et des hétéroatomes, de préférence O, S et/ou N dans la chaîne de carbone, et leurs mélanges.
  26. Procédé selon l'une quelconque des revendications 21 à 25,
    caractérisé en ce
    que l'oligomère et/ou le polymère organique est constitué de monomères présentant les fonctionnalités choisies dans le groupe comprenant les groupes amino, hydroxy, thiol, époxy, acrylate, méthacrylate, vinyle, allyle, alcényle, alcinyle, carboxy, carboxylanhydride, isocyanate, cyanate, uréido et carbamate et leurs mélanges.
  27. Procédé selon l'une quelconque des revendications 21 à 25,
    caractérisé en ce
    que l'oligomère et/ou le polymère organique réactif est choisi dans le groupe comprenant des polyacrylates, polyméthacrylates, polyéthers, polyesters, polyamines, polyamides, polyols, polyuréthanes et polyoléfines et leurs mélanges, et éventuellement étant convertis pour activation avant l'addition dans le mélange réactionnel avec un agent de réticulation organique.
  28. Procédé selon l'une quelconque des revendications 18 à 27,
    caractérisé en ce
    que le composant organique réactif est formé avant l'addition, en convertissant un ou plusieurs agents de réticulation organiques avec des groupes R1 réactifs, éventuellement en ajoutant des initiateurs de polymérisation, et ensuite sont ajoutés.
  29. Procédé selon la revendication 21,
    caractérisé en ce
    que l'oligomère et/ou le polymère organique réactif est choisi dans le groupe comprenant les polyéthylène-imines modifiées par trialcoxysilane et les polyéthylène-oxyde-uréthanes modifiés par aminosilane.
  30. Procédé selon la revendication 21,
    caractérisé en ce
    que l'oligomère et/ou le polymère organique réactif est choisi dans le groupe comprenant les polyacrylates, polyméthacrylates, polyéthers, polyesters, polyamines, polyamides, polyols, polyuréthanes et polyoléfines, ces oligomères et/ou polymères disposant de fonctions réactives.
  31. Procédé selon l'une quelconque des revendications 18 à 30,
    caractérisé en ce
    que, avant, pendant et/ou après l'addition de l'agent de réticulation organique réactif, on ajoute au moins en outre un convertisseur de réticulation organique.
  32. Procédé selon l'une quelconque des revendications 18 à 31,
    caractérisé en ce
    que, avant l'application de la couche mixte anorganique / organique, on applique sur le substrat plaquettaire, une ou plusieurs couches essentiellement purement anorganiques et/ou essentiellement purement organiques.
  33. Procédé selon l'une quelconque des revendications 18 à 32,
    caractérisé en ce
    qu'après l'application de la couche mixte anorganique / organique, on applique une ou plusieurs couches essentiellement purement anorganiques et/ou essentiellement purement organiques.
  34. Procédé selon l'une quelconque des revendications 18 à 33,
    caractérisé en ce
    que l'on applique comme couche la plus extérieure, une couche présentant un ou plusieurs agents de modification de surface.
  35. Procédé selon l'une quelconque des revendications 18 à 34,
    caractérisé en ce
    que l'on utilise comme milieu réactionnel, des solutions aqueuses et/ou alcooliques et/ou des mélanges de solvants.
  36. Procédé selon l'une quelconque des revendications 19 à 35,
    caractérisé en ce
    que la température réactionnelle lors des étapes (b) à (e) se situe dans une plage d'environ 0 °C à environ 100 °C, de préférence d'environ 10 °C à environ 80 °C.
  37. Procédé selon l'une quelconque des revendications 19 à 36,
    caractérisé en ce
    que le pH lors des étapes (b) à (e) se situe dans une plage de 1,5 à 12, de préférence de 6 à 10.
  38. Utilisation du pigment à lustre nacré plaquettaire selon l'une quelconque des revendications 1 à 17 dans les vernis, peintures, encres d'impression, vernis en poudre, peintures pour bâtiments, plastiques, encres d'impression de sécurité, céramique, verre ou préparations cosmétiques.
  39. Utilisation d'un pigment à lustre nacré plaquettaire selon l'une quelconque des revendications 1 à 17, comme marqueur laser.
EP07722891A 2006-02-24 2007-02-22 Pigments de lustre perlaire revetus de couches mixtes inorganiques/organiques et leur procede de production Not-in-force EP1874874B2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102006009131A DE102006009131A1 (de) 2006-02-24 2006-02-24 Mit anorganisch/organischen Mischschichten beschichtete Perlglanzpigmente und Verfahren zu deren Herstellung
PCT/EP2007/001515 WO2007098878A2 (fr) 2006-02-24 2007-02-22 Pigments de lustre perlaire revêtus de couches mixtes inorganiques/organiques et leur procédé de production

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EP1874874A2 EP1874874A2 (fr) 2008-01-09
EP1874874B1 EP1874874B1 (fr) 2008-11-19
EP1874874B2 true EP1874874B2 (fr) 2012-05-23

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WO (1) WO2007098878A2 (fr)

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DE10348174B4 (de) 2002-11-06 2017-02-09 Merck Patent Gmbh Oberflächenstabilisierung von Perlglanzpigmenten
EP1611209B1 (fr) * 2003-04-15 2009-12-23 MERCK PATENT GmbH Pigments a effet a modification de surface
DE10361437A1 (de) * 2003-12-23 2005-07-28 Eckart Gmbh & Co. Kg Metallpigmente mit vernetzbarer Bindemittelbeschichtung, Beschichtungszusammensetzung, Verfahren zur Herstellung der beschichteten Metallpigmente und deren Verwendung
DE102005037611A1 (de) * 2005-08-05 2007-02-15 Eckart Gmbh & Co. Kg Metalleffektpigmente mit anorganisch/organischer Mischschicht, Verfahren zur Herstellung solcher Metalleffektpigmente und deren Verwendung
DE102006009131A1 (de) * 2006-02-24 2007-09-06 Eckart Gmbh & Co.Kg Mit anorganisch/organischen Mischschichten beschichtete Perlglanzpigmente und Verfahren zu deren Herstellung
DE102007041027A1 (de) * 2007-08-29 2009-03-05 Eckart Gmbh Effektpigmente auf Basis von aus anorganisch-organischen Mischphasen gebildeten Substraten, deren Herstellung und Verwendung

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US5759255A (en) † 1996-02-07 1998-06-02 Engelhard Corporation Pearlescent pigment for exterior use
WO1999057204A1 (fr) † 1998-05-06 1999-11-11 Eckart-Werke Standard Bronzepulver-Werke Carl-Eckart Gmbh & Co. Pigments a effet recouverts d'auxiliaires d'orientation reactifs

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US20150183995A1 (en) 2015-07-02
EP1874874B1 (fr) 2008-11-19
WO2007098878A3 (fr) 2007-11-15
ATE414744T1 (de) 2008-12-15
US9790368B2 (en) 2017-10-17
WO2007098878A2 (fr) 2007-09-07
DE502007000239D1 (de) 2009-01-02
US20090252772A1 (en) 2009-10-08
DE102006009131A1 (de) 2007-09-06
US8980976B2 (en) 2015-03-17
EP1874874A2 (fr) 2008-01-09

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